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US20180171172A1 - Resin composition for forming phase-separated structure and method of producing structure including phase-separated structure - Google Patents

Resin composition for forming phase-separated structure and method of producing structure including phase-separated structure Download PDF

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Publication number
US20180171172A1
US20180171172A1 US15/843,387 US201715843387A US2018171172A1 US 20180171172 A1 US20180171172 A1 US 20180171172A1 US 201715843387 A US201715843387 A US 201715843387A US 2018171172 A1 US2018171172 A1 US 2018171172A1
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Prior art keywords
phase
block
separated structure
forming
resin composition
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Hitoshi Yamano
Takahiro Dazai
Tasuku Matsumiya
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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Assigned to TOKYO OHKA KOGYO CO., LTD. reassignment TOKYO OHKA KOGYO CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAZAI, TAKAHIRO, MATSUMIYA, TASUKU, YAMANO, HITOSHI
Publication of US20180171172A1 publication Critical patent/US20180171172A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the present invention relates to a resin composition for forming a phase-separated structure, and a method of producing a structure including a phase-separated structure.
  • phase-separated structure of the block copolymer In order to utilize the phase-separated structure of the block copolymer, it is essential to form self-organization nanostructures formed by micro phase separation only in a specific area, and arrange the self-organization nanostructures in a desired direction.
  • a processes such as graphoepitaxy for controlling a phase-separated pattern by a guide pattern and chemical epitaxy for controlling a phase-separated pattern by difference in a chemical state of substrates have been proposed (for example, refer to Proceedings of SPIE, Vol. 7637, 76370 G-1 to 11 (2010)).
  • the block copolymer forms a structure having a regular periodic structure by phase separation.
  • the “period of a structure” means a period of the phase structure observed when the structure including the phase-separated structure is formed, and refers to a sum of lengths of the respective phases incompatible with each other.
  • the period (L0) of the structure corresponds to a distance (pitch) between centers of two adjacent cylinder structures.
  • the period (L0) of the structure has been known to be determined by the intrinsic polymerization properties such as a degree of polymerization N, and an interaction parameter ⁇ of Flory-Huggins. That is, the larger a product “ ⁇ N” of ⁇ and N, the larger mutual repulsion between different blocks in the block copolymer. For this reason, when a relationship of ⁇ N>10 (hereinafter referred to as “intensity separation limit point”) is established, it is more likely that the repulsion between different types of blocks in the block copolymer is large, and the phase separation occurs.
  • the period of the structure is approximately N 2/3 ⁇ 1/6 , and the relationship of Expression (1) is established. That is, the period of the structure is proportional to the degree of polymerization N correlated with the molecular weight and the molecular weight ratio between different blocks.
  • L0 represents a period of the structure.
  • a represents a parameter indicating the size of the monomer.
  • N represents a degree of polymerization.
  • ⁇ represents an interaction parameter, in which the larger this value, the higher the phase-separation performance.
  • the periodic structure which the block copolymer forms varies the form such as a cylinder (columnar phase), a lamella (plate phase), and a sphere (spherical phase) depending on the volume ratio of the polymer components, and the period depends on the molecular weight.
  • a method for increasing the molecular weight of the block copolymers can be considered in order to form the structure of a relatively large period (L0) by utilizing the phase-separated structure formed by the self-organization of the block copolymers.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition for forming a phase-separated structure, which is capable of satisfactorily forming a phase-separated structure, and a method of producing a structure including a phase-separated structure using the aforementioned resin composition.
  • the present invention adopts the following configuration.
  • a first aspect of the present invention is to provide a resin composition for forming a phase-separated structure including a block copolymer in which a hydrophilic block and a hydrophobic block are bonded to each other, and a solvent component (S) containing an organic solvent (S1) having a boiling point of 200° C. or higher.
  • a second aspect of the present invention is to provide a method of producing a structure including a phase-separated structure, the method including apllying the resin composition for forming a phase-separated structure of the first aspect to a support to form a layer including the block copolymer, and phase-separating the layer including the block copolymer.
  • a resin composition for forming a phase-separated structure which is capable of satisfactorily forming a phase-separated structure, and a method of producing a structure including a phase-separated structure using the aforementioned resin composition.
  • FIG. 1 is a schematic process diagram illustrating an exemplary embodiment of a method of producing a structure including a phase-separated structure according to the present invention.
  • FIG. 2 is a diagram illustrating an exemplary embodiment of an optional step.
  • FIG. 3 is a schematic process diagram illustrating an exemplary embodiment of a method of producing a structure including a phase-separated structure according to the present invention.
  • FIG. 4 is a diagram illustrating an exemplary embodiment of an optional step.
  • aliphatic is a relative concept with respect to aromatic, and is defined as a group, a compound, or the like having no aromaticity.
  • Alkyl group is assumed to contain a linear, branched, or cyclic monovalent saturated hydrocarbon group unless otherwise noted. The same is true for an alkyl group in an alkoxy group.
  • Alkylene group is assumed to contain a linear, branched, and cyclic divalent saturated hydrocarbon group unless otherwise noted.
  • Halogenated alkyl group is a group obtained by substituting a portion or all of the hydrogen atoms in an alkyl group with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Fluorinated alkyl group or “fluorinated alkylene group” means a group obtained by substituting a portion or all of the hydrogen atoms in an alkyl group or an alkylene group with a fluorine atom.
  • Constuting unit means a monomer unit constituting a polymer compound (a resin, a polymer, or a copolymer).
  • the phrase “may have a substituent” means both a case of substituting a hydrogen atom (—H) with a monovalent group and a case of substituting a methylene group (—CH 2 —) with a divalent group.
  • Exposure is a concept including radiation irradiation in general.
  • Constuting unit derived from acrylic ester means a constituting unit formed by cleavage of an ethylenic double bond of the acrylic ester.
  • “Acrylic ester” is a compound obtained by substituting a hydrogen atom at a carboxy group terminal of an acrylic acid (CH 2 ⁇ CH—COOH) with an organic group.
  • the acrylic ester may be obtained by substituting a hydrogen atom bonded to an ⁇ -position carbon atom with a substituent.
  • the substituent (R ⁇ 0 ) with which the hydrogen atom bonded to the ⁇ -position carbon atom is substituted is an atom other than the hydrogen atom or a group, and examples thereof include an alkyl group having 1 to 5 carbon atoms and a halogenated alkyl group having 1 to 5 carbon atoms.
  • the acrylic ester includes itaconic diester obtained by substituting the substituent (R ⁇ 0 ) with a substituent containing an ester bond, and ⁇ -hydroxyacrylic ester obtained by substituting the substituent (R ⁇ 0 ) with a group modified with a hydroxyalkyl group or a hydroxyl group thereof.
  • the ⁇ -position carbon atoms in the acrylic ester is a carbon atom to which a carbonyl group of an acrylic acid is bonded unless otherwise noted.
  • acrylic ester obtained by substituting the hydrogen atom bonded to a ⁇ -position carbon atom with a substituent may be referred to as ⁇ -substituted acrylic ester.
  • both of the acrylic ester and the ⁇ -substituted acrylic ester may be referred to as “( ⁇ -substituted) acrylic ester”.
  • Constuting unit derived from hydroxystyrene means a constituting unit formed by cleavage of an ethylenic double bond of hydroxystyrene.
  • Constuting unit derived from a hydroxystyrene derivative means a constituting unit formed by cleavage of an ethylenic double bond of a hydroxystyrene derivative.
  • “Hydroxystyrene derivative” includes those obtained by substituting an ⁇ -position hydrogen atom of hydroxystyrene with other substituents such as an alkyl group and a halogenated alkyl group, and derivatives thereof.
  • the derivatives include a derivative obtained by substituting a hydrogen atom of a hydroxyl group of hydroxystyrene in which the ⁇ -position hydrogen atom may be substituted with a substituent with an organic group; and a derivative in which a substituent other than the hydroxyl group is bonded to a benzene ring of hydroxystyrene in which ⁇ -position hydrogen atom may be substituted with a substituent.
  • the ⁇ -position ( ⁇ -position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise noted.
  • “Styrene” is a concept including styrene and those obtained by substituting an ⁇ -position hydrogen atoms in the styrene with other substituents other than an alkyl group and a halogenated alkyl group.
  • “Styrene derivative” is a concept including those obtained by substituting the ⁇ -position hydrogen atoms in the styrene with other substituents such as an alkyl group and a halogenated alkyl group, and the derivatives thereof.
  • the derivatives include a derivative in which a substituent is bonded to a benzene ring of hydroxystyrene in which the ⁇ -position hydrogen atom may be substituted with a substituent.
  • the ⁇ -position ( ⁇ -position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise noted.
  • Constuting unit derived from the styrene and “constituting unit derived from the styrene derivative” mean constituting units formed by cleavage of an ethylenic double bond of the styrene or the styrene derivative.
  • the alkyl group as the ⁇ -position substituent is preferably a linear or branched alkyl group, and specifically, examples thereof include an alkyl group having 1 to 5 carbon atoms (a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group).
  • halogenated alkyl group as the ⁇ -position substituent include a group obtained by substituting a portion or all of the hydrogen atoms in “the alkyl group as the ⁇ -position substituent” with a halogen atom.
  • halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and particularly, a fluorine atom is preferable.
  • hydroxyalkyl group as the ⁇ -position substituent include a group obtained by substituting a portion or all of the hydrogen atoms in the “alkyl group as the ⁇ -position substituent” with a hydroxyl group.
  • the number of the hydroxyl groups in the hydroxyalkyl group is preferably of 1 to 5, and is most preferably 1.
  • a resin composition for forming a phase-separated structure includes a block copolymer in which a hydrophilic block and a hydrophobic block are bonded to each other, and a solvent component (S) containing an organic solvent (S1) having a boiling point of 200° C. or higher.
  • the block copolymer is a polymer in which a plurality of kinds of blocks are bonded to each other (a partial constituting component in which the same kinds of constituting units are repeatedly bonded).
  • the blocks constituting the block copolymer may be of two kinds, or of three or more kinds.
  • the block copolymer in the embodiment is a block copolymer in which a hydrophilic block and a hydrophobic block are bonded to each other.
  • a hydrophilic block is a block having a relatively high affinity with water as compared with other blocks among a plurality of blocks constituting a block copolymer.
  • a polymer (p1) constituting the hydrophilic block is composed of a constituting unit having relatively high affinity with water as compared with a polymer (p2) constituting the other block.
  • the hydrophobic block is a block other than the hydrophilic block among the plurality of blocks constituting the block copolymer.
  • the polymer (p2) constituting the hydrophobic block is composed of a constituting unit having a relatively low affinity with water as compared with the polymer (p1).
  • the plurality of blocks constituting the block copolymer are not particularly limited as long as it is a combination that occurs the phase separation, and are preferably a combination of blocks incompatible with each other. Further, as the blocks, it is preferable to use a combination in which a phase formed of at least one kind of block among the plurality of kinds of blocks constituting the block copolymer can be easily and selectively removed as compared with phases formed of other kinds of blocks. As the combination which can be easily and selectively removed, a block copolymer in which one or two or more kinds of blocks having an etching selectivity ratio of larger than 1 are bonded is exemplified.
  • the block copolymer examples include a block copolymer in which a block of a constituting unit having an aromatic group and a block of a constituting unit derived from ( ⁇ -substituted) acrylic ester are bonded to each other; a block copolymer in which the block of the constituting unit having an aromatic group and a block of a constituting unit derived from ( ⁇ -substituted) acrylic acid are bonded to each other; a block copolymer in which the block of the constituting unit having an aromatic group and a block of a constituting unit derived from siloxane or its derivatives are bonded to each other; a block copolymer in which a block of a constituting unit derived from alkylene oxide and the block of the constituting unit derived from ( ⁇ -substituted) acrylic ester are bonded to each other; a block copolymer in which the block of the constituting unit derived from alkylene oxide and the block of the constituting unit derived from ( ⁇ -sub
  • the constituting unit having an aromatic group examples include a constituting unit having an aromatic group such as a phenyl group and a naphthyl group. Among them, a constituting unit derived from styrene or a derivative thereof is preferable.
  • styrene or the derivative thereof examples include ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, 4-vinylbenzyl chloride, 1-vinylnaphthalene, 4-vinylbiphenyl, 1-vinyl-2-pyrrolidone, 9-vinylanthracene, and vinyl pyridine.
  • the ( ⁇ -substituted) acrylic acid means one or both of an acrylic acid and ones in which a hydrogen atom bonded to an ⁇ -position carbon atom in the acrylic acid is substituted with a substituent.
  • substituents include an alkyl group having 1 to 5 carbon atoms.
  • Examples of the ( ⁇ -substituted) acrylic acid include an acrylic acid and a methacrylic acid.
  • ( ⁇ -Substituted) acrylic ester means one or both of acrylic ester and ones in which a hydrogen atom bonded to an ⁇ -position carbon atom in the acrylic ester is substituted with a substituent.
  • substituents include an alkyl group having 1 to 5 carbon atoms.
  • acrylic ester examples include acrylic ester such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, anthracene acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethane acrylate, and propyl trimethoxysilane acrylate; and methacrylic ester such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, methyl methacrylate,
  • methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and t-butyl methacrylate are preferable.
  • siloxane or its derivatives examples include dimethyl siloxane, diethyl siloxane, diphenyl siloxane, and methyl phenyl siloxane.
  • alkylene oxide examples include ethylene oxide, propylene oxide, isopropylene oxide, and butylene oxide.
  • constituting unit having a silsesquioxane structure a constituting unit having a cage type silsesquioxane structure is preferable.
  • a monomer providing the constituting unit having the cage type silsesquioxane structure a compound having the cage type silsesquioxane structure and a polymerizable group is exemplified.
  • a block copolymer including the block of the constituting unit having an aromatic group and the block of the constituting unit derived from an ( ⁇ -substituted) acrylic acid or ( ⁇ -substituted) acrylic ester is preferable.
  • the ( ⁇ -substituted) acrylic acid or the block of the constituting unit derived from ( ⁇ -substituted) acrylic ester is the hydrophilic block
  • the block of the constituting unit derived from styrene is the hydrophobic block.
  • a polymer (p1) constituting the hydrophilic block is an ( ⁇ -substituted) acrylic acid polymer or an ( ⁇ -substituted) acrylic ester polymer.
  • a mass ratio of the constituting unit having an aromatic group to the constituting unit derived from the ( ⁇ -substituted) acrylic acid or the ( ⁇ -substituted) acrylic ester is preferably in a range of 60:40 to 90:10, and is further preferably in a range of 60:40 to 80:20.
  • the mass ratio of the constituting unit having an aromatic group to the constituting unit derived from the ( ⁇ -substituted) acrylic acid or the ( ⁇ -substituted) acrylic ester is preferably in a range of 35:65 to 60:40, and is further preferably in a range of 40:60 to 60:40.
  • the block copolymer examples include a block copolymer having a block of the constituting unit derived from styrene and a block of a constituting unit derived from acrylic acid, a block copolymer having a block of a constituting unit derived from styrene and a block of the constituting unit derived from methyl acrylate, a block copolymer having a block of a constituting unit derived from styrene and the block of a constituting unit derived from ethyl acrylate, a block copolymer having a block of a constituting unit derived from styrene and a block of a constituting unit derived from t-butyl acrylate, a block copolymer having a block of the constituting unit derived from styrene and a block of the constituting unit derived from a methacrylic acid, a block copolymer having a block of the constituting unit derived from
  • the polymer (p1) is a poly(acrylic acid), poly(methyl acrylate), poly(ethyl acrylate), poly(t-butyl acrylate), a poly(methacrylic acid), poly(methyl methacrylate), poly(ethyl methacrylate), poly(t-butyl methacrylate), a poly(acrylic acid), and poly(methyl acrylate), respectively.
  • the block copolymer (PS-PMMA block copolymer) the block of the constituting unit derived from styrene (PS) and the block of the constituting unit derived from methyl methacrylate (PMMA).
  • the number average molecular weight (Mn) of the block copolymer is preferably equal to or greater than 6000, is further preferably in a range of 8000 to 200000, and is still further preferably in a range of 10000 to 160000.
  • the dispersity (Mw/Mn) of the block copolymer is preferably in a range of 1.0 to 3.0, is further preferably in a range of 1.0 to 1.5, and is still further preferably in a range of 1.0 to 1.3. Note that, “Mw” represents mass average molecular weight.
  • the block copolymer may be used alone or two or more kinds thereof may be used in combination.
  • the content of the block copolymer may be adjusted depending on a thickness of a layer containing a block copolymer to be formed.
  • the resin composition for forming a phase-separated structure in the embodiment can be prepared by dissolving the block copolymer in a solvent component (S).
  • the solvent component (S) contains an organic solvent (S1) having a boiling point of 200° C. or higher.
  • the boiling point of the organic solvent (S1) is not particularly limited as long as it is 200° C. or higher, and is preferably 210° C. or higher, and is further preferably 220° C. or higher.
  • An upper limit value of the boiling point of the organic solvent (S1) is not particularly limited, but is preferably 300° C. or lower, is further preferably 280° C. or lower, and is still further preferably 250° C. or lower from the viewpoint of annealing treatment temperature or the like.
  • organic solvent (S1) any organic solvent having a boiling point of 200° C. or higher can be appropriately selected and used among known organic solvents for a film composition containing a resin as a main component.
  • Examples of the organic solvent (S1) include imidazolidinones such as 1,3-dimethyl-2-imidazolidinone (DMI); lactones such as ⁇ -methyl- ⁇ -butyrolactone and ⁇ -butyrolactone; polyhydric alcohols such as diethylene glycol and dipropylene glycol; a compound having an ester bond such as butyl diglycol diacetate, ethyl diglycol acetate, dipropylene glycol methyl ether acetate, and butylene glycol diacetate; derivatives of the polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, or polyhydric alcohols such as a compound having an ether bond such as monoalkyl ether or monophenyl ether in a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate [among them
  • organic solvent (S1) derivatives such as lactones, imidazolidinones, and polyhydric alcohols are preferable.
  • lactones a ⁇ -butyrolactone having a substituent is preferable, and as a preferable example, ⁇ -methyl- ⁇ -butyrolactone is exemplified.
  • imidazolidinones those having an alkyl group as a substituent are preferable, and as a preferable example, 1,3-dimethyl-2-imidazolidinone (DMI) is exemplified.
  • a derivative having an ether bond of propylene glycol is preferable, and a derivative having a monoalkyl ether or monophenyl ether of propylene glycol is further preferable.
  • propylene glycol 1-monophennyl ether (PhFG) and dipropylene glycol monobutyl ether (BFDG) are preferable can be exemplified.
  • the organic solvent (S1) may be used alone or two or more kinds thereof may be used in combination.
  • an interaction distance Ra S1 between a Hansen solubility parameter thereof and a Hansen solubility parameter of a polymer (p1) constituting a hydrophilic block of a block copolymer is preferably equal to or less than 6.0 MPa 0.5 .
  • Ra S1 is equal to or less than the above upper limit value, the affinity between the organic solvent (S1) and the hydrophilic block of the block copolymer is improved, and the number of defects is reduced when a pattern is formed from the phase-separated structure.
  • the range of Ra S1 is preferably in a range of 1.0 to 6.0 MPa 0.5 , is further preferably in a range of 2.0 to 6.0 MPa 0.5 , and is still further preferably in a range of 2.5 to 6.0 MPa 0.5 .
  • the Hansen solubility parameter can be calculated from a predetermined parameter based on the solubility parameter described by Charles Hansen in “Hansen Solubility Parameters: A User's Handbook” written by Charles M. Hansen, and “The CRC Handbook and Solubility Parameters and Cohesion Parameters,” (1999) edited by CRC Press (2007) and Allan F. M. Barton (1999), and an aggregation property.
  • the Hansen solubility parameter is theoretically calculated as a numerical constant and is a useful tool for predicting the ability of a solvent material to dissolve a particular solute.
  • the Hansen solubility parameter can be used as a measure of the overall strength and selectivity of a material by combining experimentally and theoretically derived three Hansen solubility parameters (that is, ⁇ D, ⁇ P, and ⁇ H).
  • a unit of the Hansen solubility parameter is denoted MPa 0.5 or (J/cc) 0.5 .
  • Ra is calculated by the following expression.
  • ⁇ d1 , ⁇ p1 , and ⁇ h1 respectively represent by ⁇ D, ⁇ P, and ⁇ H of the molecule (1).
  • ⁇ d2 , ⁇ p2 , and ⁇ h2 respectively represent ⁇ D, ⁇ P, and ⁇ H of the molecule (2).
  • the interaction distance Ra S1 between the Hansen solubility parameter of the organic solvent (S1) and the Hansen solubility parameter of the polymer (p1) can be calculated by the following expression.
  • ⁇ dS1 , ⁇ pS1 , and ⁇ hS1 respectively represent ⁇ D, ⁇ P, and ⁇ H of the organic solvent (S1).
  • ⁇ dp1 , ⁇ pp1 , and ⁇ hp1 respectively represent ⁇ D, ⁇ P, and ⁇ H of the polymer (p1).
  • Hansen solubility parameters of the organic solvent (S1) and the polymer (p1) can be calculated based on “Molecular Modeling Pro” software, version 5.1.9 (ChemSW, FairfieldCA, www.chemsw.com), or Hansen Solubility of Dynacomp Software.
  • examples of the organic solvent (S1) in which Ra S1 is equal to or less than 6.0 MPa 0.5 include DMI (Ra S1 : 3.0), PhFG (Ra S1 : 5.8), and BFDG (Ra S1 : 5.6).
  • an interaction distance Ra S1p2 between the Hansen solubility parameter of the organic solvent and a Hansen solubility parameter of a polymer (p2) constituting the hydrophobic block of the block copolymer is preferably equal to or greater than 6.0 MPa 0.5 .
  • the Ra S1p2 is preferably in a range of 6.0 to 15.0 MPa 0.5 , is further preferably in a range of 7.0 to 12.0 MPa 0.5 , and is still further preferably in a range of 8.0 to 10.0 MPa 0.5 .
  • a surface tension is preferably in a range of 10 to 100 mN/m.
  • the surface tension of the organic solvent (S1) is preferably in a range of 15 to 80 mN/m, and is further preferably in a range of 20 to 50 mN/m.
  • the solvent component (S) preferably contains a main solvent (Sm) other than the organic solvent (S1).
  • the solvent component (S) contains the main solvent (Sm)
  • the wettability at the time of coating a support with the resin composition for forming a phase-separated structure is improved.
  • any solvent may be used as long as it can dissolve the components to be used and make it into a homogeneous solution.
  • any one other than the organic solvent (S1) can be used by appropriately selecting one or two or more kinds thereof.
  • Examples of the main solvent (Sm) include lactones such as ⁇ -butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; derivatives of the polyhydric alcohols or polyhydric alcohols such as a compound having an ether bond such as monoalkyl ether of monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether, or monophenyl ether in a compound having an ester bond [among them, propylene glycol monomethyl ether acetate
  • propylene glycol monomethyl ether acetate PGMEA
  • propylene glycol monomethyl ether PGME
  • cyclohexanone PGME
  • ethyl lactate EL
  • the main solvent (Sm) a mixed solvent in which PGMEA and a polar solvent are mixed is also preferable.
  • the compounding ratio (mass ratio) may be appropriately determined in consideration of compatibility between the PGMEA and the polar solvent, and is preferably in a range of 1:9 to 9:1, and is further preferably in a range of 2:8 to 8:2.
  • the mass ratio of PGMEA:EL is preferably in a range of 1:9 to 9:1, and is further preferably in a range of 2:8 to 8:2.
  • the mass ratio of PGMEA:PGME is preferably in a range of 1:9 to 9:1, is further preferably in a range of 2:8 to 8:2, and is still further preferably in a range of 3:7 to 7:3.
  • the mass ratio of PGMEA:(PGME+cyclohexanone) is preferably in a range of 1:9 to 9:1, is further preferably in a range of 2:8 to 8:2, and is still further preferably in a range of 3:7 to 7:3.
  • the main solvent (Sm) include a mixed solvent of PGMEA or EL and ⁇ -butyrolactone, and a mixed solvent of the mixed solvent of the PGMEA and the polar solvent, and ⁇ -butyrolactone are also preferable.
  • the mass ratio of the former to the latter is preferably in a range of 70:30 to 95:5.
  • an interaction distance Ra Sm between the Hansen solubility parameters of the main solvent (Sm) and a polymer (p1) constituting a hydrophilic block of the block copolymer is preferably larger than the interaction distance Ra S1 between the Hansen solubility parameters of the organic solvent (S1) and the polymer (p1). That is, the interaction distance Ra S1 is preferably smaller than the interaction distance Ra Sm .
  • the proportion of the main solvent (Sm) in the solvent component (S) is preferably equal to or greater than 50% by mass with respect to the total mass (100% by mass) of the solvent component (S).
  • the proportion of the main solvent (Sm) in the solvent component (S) is preferably in a range of 50% to 99% by mass, is further preferably in a range of 60% to 98% by mass, and is still further preferably in a range of 70% to 97% by mass with respect to the total mass (100% by mass) of the solvent component (S).
  • the blending ratio (mass ratio) of the main solvent (Sm) and the organic solvent (S1) in the solvent component (S) is preferably in a range of 99:1 to 50:50, is further preferably in a range of 98:2 to 60:40, and is still further preferably in a range of 97:3 to 70:30.
  • the blending ratio of the main solvent (Sm) and the organic solvent (S1) is within the above range, the wettability at the time of coating a support with the resin composition for forming a phase-separated structure is improved, and defects at the time of forming a pattern are reduced, thereby improving lithography properties such as CDU.
  • the proportion of the solvent component (S) in the resin composition for forming a phase-separated structure is not particularly limited, and is appropriately set according to the coating film thickness at a coatable concentration.
  • the solvent component (S) is used such that the solid content concentration is within the range of 0.2% to 70% by mass, and is preferably in a range of 0.2% to 50% by mass.
  • the resin composition for forming a phase-separated structure in the embodiment can appropriately contain, in addition to the above-described block copolymer and the solvent component (S), miscible additives such as an additional resin for improving the performance of an undercoating agent layer, a surfactant for improving coatability, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a sensitizer, a base proliferator, and a basic compound, as necessary.
  • miscible additives such as an additional resin for improving the performance of an undercoating agent layer, a surfactant for improving coatability, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, a sensitizer, a base proliferator, and a basic compound, as necessary.
  • the solvent component (S) contains the organic solvent (S1) having a boiling point of 200° C. or higher, it is possible to form an excellent phase-separated structure.
  • the solvent component (S) contains the organic solvent (S1), the affinity with the solvent component (S) and the hydrophilic block of the block copolymer is improved.
  • phase-separated structure when forming of the phase-separated structure, generally, an excellent phase-separated structure is formed in the vicinity of a central portion of an area which the resin composition for forming a phase-separated structure is applied, as the edge becomes closer, the phase-separated structure is less likely to be formed.
  • the resin composition for forming a phase-separated structure in the embodiment even in the vicinity of the edge of the area which the resin composition for forming a phase-separated structure is applied, it is possible to form an excellent phase-separated structure.
  • a method of producing a structure including a phase-separated structure includes a step (hereinafter, referred to as “Step (i)”) of applying the resin composition for forming a phase-separated structure according to the first aspect to a support to form a layer including a block copolymer, and a step (hereinafter, referred to as “Step (ii)”) of phase-separating the layer including the block copolymer.
  • FIG. 1 illustrates an exemplary embodiment of the method of producing a structure including a phase-separated structure.
  • an undercoating agent is applied to a support to form an undercoating agent layer 2 ( FIG. 1 (I)).
  • the resin composition for forming a phase-separated structure is applied to the undercoating layer 2 to form a layer (BCP layer) 3 including a block copolymer ( FIG. 1 (II); Step (i)).
  • the BCP layer 3 is phase-separated into a phase 3 a and a phase 3 b by heating and annealing treatment ( FIG. 1 (III); Step (ii)).
  • a structure 3 ′ including a phase-separated structure is produced on the support 1 on which the undercoating agent layer 2 is formed.
  • Step (i) the BCP layer 3 is formed on the support 1 by using the resin composition for forming a phase-separated structure.
  • the support is not particularly limited as long as the resin composition for forming a phase-separated structure can be applied to its surface.
  • the support examples include a substrate made of a metal such as silicon, copper, chromium, iron, and aluminum, a substrate made of an inorganic material such as glass, titanium oxide, silica, and mica, an acrylic plate, and a substrate made of an organic compound such as polystyrene, cellulose, cellulose acetate, and phenol resin.
  • a metal such as silicon, copper, chromium, iron, and aluminum
  • a substrate made of an inorganic material such as glass, titanium oxide, silica, and mica
  • an acrylic plate an acrylic plate
  • an organic compound such as polystyrene, cellulose, cellulose acetate, and phenol resin.
  • the size and shape of the support are not particularly limited.
  • the support does not necessarily have a smooth surface and the support of various materials and shapes can be selected appropriately.
  • various shapes such as a substrate having a curved surface, a flat plate having an uneven surface, a thin plate shape, and the like can be variously used.
  • an inorganic and/or an organic film may be provided on the surface of the support.
  • the inorganic film include an inorganic antireflection film (inorganic BARC).
  • the organic film include an organic antireflection film (organic BARC).
  • the surface of the support 1 may be cleaned.
  • the support 1 can be more effectively coated with the resin composition for forming a phase-separated structure or the undercoating agent.
  • a cleaning treatment a conventionally known method can be used, and examples thereof include an oxygen plasma treatment, a hydrogen plasma treatment, an ozone oxidation treatment, an acid alkali treatment, and a chemical modification treatment.
  • the support is immersed in an acid solution such as a sulfuric acid/hydrogen peroxide solution, and then washed with water and dried. After that, the BCP layer 3 or the undercoating agent layer 2 is formed on the surface of the support.
  • a neutralization treatment is a treatment to modify the support surface to have affinity with any polymer constituting the block copolymer. By performing the neutralization treatment, it is possible to prevent only a phase of a specific polymer to come into contact with the support surface by the phase separation.
  • the undercoating agent layer 2 is formed on the surface of the support 1 by using an undercoating agent having the affinity with any polymer constituting the block copolymer.
  • a conventionally known resin composition used for forming a thin film can be appropriately selected and used in accordance with the type of the polymer constituting the block copolymer.
  • undercoating agent examples include a composition containing a resin having all constituting units of each polymer constituting the block copolymer, and a composition containing a resin having constituting units with high affinity with each polymer constituting the block copolymer.
  • PS-PMMA block copolymer including a block of the constituting unit derived from styrene (PS) and a block of the constituting unit derived from methyl methacrylate (PMMA), as the undercoating agent
  • a resin composition containing both PS and PMMA as a block or a compound or a composition containing both a portion having high affinity with an aromatic ring or the like and a portion having high affinity with a highly polar functional group or the like.
  • Examples of the resin composition containing both PS and PMMA as a block include a random copolymer of PS and PMMA, and an alternating polymer of PS and PMMA (a copolymer in which the respective monomers are alternately copolymerized).
  • composition containing both a portion having the high affinity with PS and a portion having the high affinity with PMMA for example, a resin composition obtained by polymerizing at least a monomer having an aromatic ring and a monomer having a highly polar substituent as a monomer can be exemplified.
  • Examples of the monomer having an aromatic ring include a monomer having a group in which one hydrogen atom has been removed from an aromatic hydrocarbon ring, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group, or a monomer having a heteroaryl group in which a part of the carbon atoms constituting the ring of the aforementioned groups is substituted with a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.
  • a monomer having a group in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group
  • Examples of the monomer having a highly polar substituent include a monomer having a hydroxyalkyl group in which a part of hydrogen atoms of a trimethoxysilyl group, a trichlorosilyl group, a carboxy group, a hydroxyl group, a cyano group, and an alkyl group is substituted with a fluorine atom.
  • Examples of other compounds containing both the portion with high affinity with PS and the portion with high affinity with PMMA include a compound containing both an aryl group such as phenethyltrichlorosilane and a highly polar substituent, and a compound containing both an alkyl group such as a silane compound and a highly polar substituent.
  • examples of the undercoating agent include a photosensitive resin composition such as a heat-polymerizable resin composition, a positive resist composition, and a negative resist composition.
  • undercoating agent layers can be formed by using a conventional method.
  • a method of forming the undercoating agent layer 2 by applying the undercoating agent to the support 1 is not particularly limited, and the undercoating agent layer 2 can be formed by using a conventionally known method.
  • the undercoating agent layer 2 can be formed by forming a coated film obtained by coating the support 1 with undercoating agent using a spin coater and a spinner through a conventionally known method, and then drying the coated film.
  • a method of drying the coated film may be any method as long as the solvent contained in the undercoating agent can be volatilized, and for example, a method of baking the film is exemplified.
  • a baking temperature is preferably in a range of 80° C. to 300° C., is further preferably in a range of 180° C. to 270° C., and is still further preferably in a range of 220° C. to 250° C.
  • the baking time is preferably in a range of 30 to 500 seconds, and is further preferably in a range of 60 to 400 seconds.
  • the thickness of the undercoating agent layer 2 after drying the coated film is preferably in a range of 10 to 100 nm, and is further preferably in a range of 40 to 90 nm.
  • the BCP layer 3 is formed on the undercoating agent layer 2 by using the resin composition for forming a phase-separated structure.
  • the method of forming the BCP layer 3 on the undercoating agent layer 2 is not particularly limited, and examples thereof include a method of forming a coated film by coating the undercoating agent layer 2 with the resin composition for forming a phase-separated structure using a spin coater and a spinner through a conventionally known method, and then drying the coated film.
  • the method of drying the coated film of the resin composition for forming a phase-separated structure may be any method as long as an organic solvent component which is contained in the resin composition for forming a phase-separated structure can be volatilized, and for example, a shake-off drying method, and a baking method are exemplified.
  • the thickness of the BCP layer 3 may be a thickness sufficient for the phase separation to occur, and is preferably in a range of 10 to 100 nm, and is further preferably in a range of 30 to 80 nm in consideration of the type of the support 1 , the periodic size of the structure of the phase-separated structure to be formed, or the uniformity of a nano-structure.
  • the thickness of the BCP layer 3 is preferably in a range of 20 to 100 nm, and is further preferably in a range of 30 to 80 nm.
  • the thickness of the BCP layer 3 is preferably in a range of 10 to 100 nm, and is further preferably in a range of 30 to 80 nm.
  • Step (ii) the BCP layer 3 formed on the support 1 is phase-separated.
  • a phase-separated structure is formed such that at least a part of the surface of the support 1 is exposed by selective removal of the block copolymer. That is, a structure 3 ′ including a phase-separated structure which is phase-separated into a phase 3 a and a phase 3 b is formed on the support 1 .
  • the temperature condition of the annealing treatment it is preferable that the temperature is equal to or higher than a glass transition temperature of the block copolymer to be used, and is lower than a thermal decomposition temperature.
  • the temperature condition of the annealing treatment the temperature is preferably in a range of 100° C. to 400° C., is further preferably in a range of 120° C. to 350° C., and is particularly preferably in a range of 150° C. to 300° C.
  • the heating time is preferably in a range of 30 to 3600 seconds, and is further preferably in a range of 120 to 600 seconds.
  • the annealing treatment is preferably performed in a gas having low reactivity such as nitrogen.
  • the method of producing a structure including a phase-separated structure according to the present invention is not limited to the above-described embodiment, and may have steps (optional steps) other than Steps (i) to (ii).
  • Step (iii) of selectively removing a phase formed of at least one kind of block among the plurality of kinds of blocks constituting the block copolymer in the BCP layer 3 , and a guide pattern forming step.
  • Step (iii) the phases (phase 3 a, phase 3 b ) formed of at least one kind of block among the plurality of kinds of blocks constituting the block copolymer in the BCP layer 3 formed on the undercoating agent layer 2 are selectively removed. As a result, a fine pattern (high molecular nano-structure) is formed.
  • Examples of a method of selectively removing the phase formed of the block include a method of performing an oxygen plasma treatment on the BCP layer and a method of performing a hydrogen plasma treatment.
  • a block that is not selectively removed is referred to as a P A block
  • a block that is selectively removed is referred to as a P B block.
  • the phase formed of PMMA is selectively removed by performing an oxygen plasma treatment, a hydrogen plasma treatment, or the like on the phase-separated layer.
  • a PS part is the P A block
  • a PMMA part is the P B block.
  • FIG. 2 illustrates an exemplary embodiment of Step (iii).
  • the phase 3 a is selectively removed by performing the oxygen plasma treatment on the structure 3 ′ prepared on the support 1 in Step (ii), and a pattern (high molecular nano-structure) formed of the separated phase 3 b is formed.
  • the phase 3 b is a phase formed of the P A block and the phase 3 a is a phase formed of the P B block.
  • the support 1 with the pattern formed by the phase separation of the BCP layer 3 can be used as it is, but it is also possible to change the shape the pattern (high molecular nano-structure) of the support 1 by further heating.
  • the temperature condition for heating equal to or higher than a glass transition temperature of the block copolymer to be used, and is preferably lower than a thermal decomposition temperature.
  • the heating is preferably performed in a gas having low reactivity such as nitrogen.
  • the method of producing a structure including a phase-separated structure according to the present embodiment may include a step (guide pattern forming step) of providing a guide pattern on a support or an undercoating agent layer. With this, it possible to control an array structure of the phase-separated structure.
  • the guide pattern may be provided on the undercoating agent layer 2 .
  • the surface of the guide pattern has the affinity with any of the polymers constituting the block copolymer, it is likely to form a cylinder-like or lamellar phase-separated structure oriented in the direction perpendicular to the support surface.
  • the guide pattern can be formed, for example, by using a resist composition.
  • the resist composition for forming the guide pattern among the resist composition generally used for forming the resist pattern and its modification, those having affinity with any one of polymers constituting the block copolymer can be appropriately selected and used.
  • the resist composition may be any one of a positive resist composition which forms a positive pattern in which a resist film exposed portion is dissolved and removed, and a negative resist composition which forms a negative pattern in which a resist film unexposed portion is dissolved and removed, and is preferably the negative resist composition.
  • the negative resist composition contains, for example, an acid generator component and a base component in which the solubility of a developer containing an organic solvent is reduced by the action of an acid, and a resist composition in which the base component contains a resin component having a constituting unit that decomposes by the action of an acid to increase the polarity is preferable.
  • the annealing treatment is performed to cause the phase separation. Therefore, as the resist composition for forming a guide pattern, resist composition capable to form a resist film excellent in the solvent resistance and heat resistance is preferable.
  • a guide pattern may be formed by forming a spin-on-carbon (SOC) layer, a silicon hard mask layer, or the like on the support, and etching these layers.
  • SOC spin-on-carbon
  • a resist pattern by a resist composition is formed on the SOC layer or the silicon hard mask layer formed on the support, and the resist pattern is used as a mask so as to form a guide pattern by etching the SOC layer or the silicon hard mask layer with fluorine-based gas or oxygen-based gas.
  • FIG. 3 illustrates an exemplary embodiment of producing a structure including a phase-separated structure using the guide pattern of the SOC layer, the silicon hard mask layer, or the like.
  • the undercoating agent layer 2 is formed by applying the undercoating agent to the support 1 , on which a recess formed by a guide pattern 4 ( FIG. 3 (I)).
  • the BCP layer 3 is formed by applying the resin composition for forming a phase-separated structure to the undercoating agent layer 2 so as to fill the recess formed by the guide pattern 4 ( FIG. 3 (II)).
  • the above step corresponds to Step (I) described above, and it may be performed in the same way as the example described in the above-described “[Step (i)]” except that the support 1 having the guide pattern 4 is used.
  • Step (ii) corresponds to Step (ii) described above and may be performed in the same way as the example described in the above-described “[Step (ii)]”.
  • FIG. 4 illustrates an exemplary embodiment in which the phase 3 a is selectively removed in the structure including a phase-separated structure produced by using the guide pattern as described above.
  • the selective removal of the phase 3 a corresponds to Step (iii) described above and may be performed in the same manner as the example described in “Regarding Step (iii)”.
  • a pattern is formed on the support 1 .
  • the shape of the guide pattern 4 patterns of various shapes such as a hole pattern and a line pattern can be formed on the support 1 .
  • BCP-(1) Block copolymer of polystyrene (PS block) and polymethyl methacrylate (PMMA block) [Mn: PS of 82 k, PMMA of 29 k, 111 k in total; Composition ratio (mass ratio) of PS/PMMA 74/26; Dispersity of 1.02]
  • Ra PS Interaction distance Ra between Hansen solubility parameter of solvent and Hansen solubility parameter of polystyrene.
  • Ra PMMA Interaction distance Ra between Hansen solubility parameter of solvent and Hansen solubility parameter of polymethyl methacrylate.
  • a spin-on-carbon (SOC) layer with a film thickness of 100 nm and a silicon hard mask film with a film thickness of 10 nm were formed in this order. Then, a resist film was formed on the silicon hard mask film. The resist film was subjected to an exposure treatment with ArF light of 193 nm using an ArF exposure apparatus and then developed so as to form a desired resist pattern.
  • SOC spin-on-carbon
  • the resist film having the resist pattern was used as a mask, and then the silicon hard mask film was etched with fluorine gas. As a result, the pattern was transferred to the silicon hard mask film.
  • the formed guide pattern was a trench pattern with a pitch of 180 nm, and 20 kinds of guide patterns with a trench width in a range of 55 to 65 nm, which were different from each other by 0.5 nm increments, were obtained.
  • the guide pattern of each trench width has a pattern area of 5 ⁇ m ⁇ 8 ⁇ m.
  • a silicon wafer on which the guide pattern was formed as described above was coated with the following undercoating agent by spin coating (rotational speed: 1500 rpm, 30 seconds), and then the coated silicon wafer was baked in atmosphere at 90° C. for one minute, and dried so as to form an undercoating agent layer having a thickness of 100 nm.
  • a terminally modified polystyrene resin PGMEA solution (resin concentration 3% by mass) was used.
  • the undercoating agent layer was rinsed with PGMEA for 60 seconds to remove the polymer such as unreacted areas. After that, baking was performed at 250° C. for 60 seconds. After baking, the film thickness of the undercoating agent layer formed on the wafer was 2 nm.
  • the resin compositions for forming a phase-separated structure (Solid content concentration: 1.2% by mass) in Examples were spin-coated (rotation speed: 1500 rpm, 30 seconds) so as to cover the undercoating agent layer formed on the wafer, the coated film were shake-off dried, and thereby a PS-PMMA block copolymer layer having a thickness of 30 nm was formed.
  • the annealing treatment was performed by heating at 250° C. for 300 seconds in a nitrogen stream to phase-separate the PS-PMMA block copolymer layer into a phase formed of PS and a phase formed of PMMA so as to form a structure including the phase-separated structure.
  • the wafer on which the phase-separated structure is prepared was subjected to an oxygen plasma treatment so as to selectively remove a phase formed of PMMA.
  • a total of 20 shots of hole patterns were formed by the above-described method with 20 kinds of guide patterns with a trench width in a range of 55 to 65 nm, which were different from each other by 0.5 nm increments.
  • the 20 shots of hole patterns were observed, and the hole formed for each pattern was evaluated.
  • the number of patterns in which 90% or more holes can be formed without defects was counted and set as the value of the process window.
  • defect refers to a state in which there is no hole to be present or a state in which a plurality of holes to be separated are connected.
  • a CH pattern was observed from the sky with a scanning electron microscope SEM (SU 8000, manufactured by Hitachi High-Technologies Corporation), and a hole diameter (nm) of 100 holes in the CH pattern was measured.

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JPWO2016133115A1 (ja) * 2015-02-20 2017-11-30 Jsr株式会社 自己組織化膜の形成方法、パターン形成方法及び自己組織化膜形成用組成物

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US20210363691A1 (en) * 2020-05-22 2021-11-25 Konica Minolta, Inc. Pretreatment liquid, pretreated fabric and method for producing the same, and image forming method
US11692303B2 (en) * 2020-05-22 2023-07-04 Konica Minolta, Inc. Pretreatment liquid, pretreated fabric and method for producing the same, and image forming method
CN115667381A (zh) * 2020-05-26 2023-01-31 日产化学株式会社 进行了垂直相分离的嵌段共聚物层

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